Russian Geology and Geophysics Vol. 47, No. 12, pp.

1344-1359, 2006

Geologiya i Geofizika UDC 550.41,546.59+;553.499

PHYSICOCHEMICAL MODELS FOR ORE FORMATION PROCESSES AT MERCURY DEPOSITS

A.A. Obolensky, L.V. Gushchina, and A.S. Borisenko Institute of Geology and Mineralogy, Siberian Branch of the RAS, 3 prosp. Akad. Koptyuga, Novosibirsk, 630090, Russia

We report results of computer modeling of physicochemical ore formation processes at mercury deposits accumulated during the development of secondary-hydrothermal and mixed-fluid ore-forming systems. Exogenous chloride brines, oil waters of artesian basins, and petroleum pools are shown to serve as secondary mercury reservoirs and geochemical barriers. Modeling of possible mechanisms of mercury transfer and deposition in the form of cinnabar (-HgS) was performed for ore-forming solutions of different compositions. Four main thermodynamic models have been constructed using the Chiller program: (1) simple cooling (cooling only), for recent thermal springs, (2) mixing of high-chloride hydrothermal solutions with cold hydrosulfuric waters (mixing model), for telethermal deposits, (3) isoenthalpic boiling (P = f(T)), and (4) solutionrock interaction (rock titration model). Mercury deposits, ore-forming systems, composition of hydrothermal solutions, forms of mercury transfer, metal-bearing capacity of solutions, thermodynamic modeling

INTRODUCTION Study of geology, genesis, and regularities of mercury-deposit localization was one of the main avenues of research of Academician V.A. Kuznetsov. Beginning with studying the Chagan-Uzun deposit [Kuznetsov, 1934] and having discovered the Aktash deposit in Gorny Altai [Kuznetsov and Mukhin, 1936] and others in Kuznetsk Alatau and Gornaya Shoria [Kuznetsov, 1939, 1940], he substantiated the concept of the West Siberian [Kuznetsov, 1943] and, later (after the discovery and study of Hg deposits in Tuva, West and East Sayans), Altai-Sayan [Kuznetsov, 1958] mercury provinces. Having established the relationship of Central Asian Hg deposits with Mesozoic tectonomagmatic activity, Kuznetsov recognized the Central Asian mercury belt as a global geologic structure controlling the localization of Hg deposits [Kuznetsov, 1974]. Along with metallogeny problems, classification of mercury deposits was developed on the basis of recognized ore associations [Kuznetsov et al., 1996], and the key genesis problems were studied, such as sources of ore matter [Kuznetsov and Obolensky, 1970], mineral composition of ores, types of metasomatic wallrocks [Kuznetsov et al., 1978], relationship of Hg deposits with magmatism, nature and sources of ore-forming hydrothermal solutions [Obolensky et al., 1979], and physicochemical conditions of mercury transfer and deposition established in thermobarogeochemical studies of fluid inclusions and thermodynamic modeling [Belevantsev et al., 1982]. In recent years, types of low-temperature hydrothermal ore-forming systems and their evolution in various geodynamic settings [Borisenko, 1999; Obolensky et al., 1999; Obolenskiy and Naumov, 2003] and conditions of localization of large mercury deposits [Distanov et al., 1998; Borisenko et al., 2005, 2006a] have been described. In this paper we present results of computer modeling of ore formation processes at the main types of Hg deposits. As we established earlier, such deposits are localized in structures of various geodynamic settings [Obolenskiy and Naumov, 2003]: 1. On active continental margins: In suprasubduction fault zones and in obducted oceanic crust in frontal parts of subduction zones
2006 IGM, SIBERIAN BRANCH OF THE RAS

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(Californian type). This type includes the New Almaden and New Idria listwaenite-cinnabar Hg deposits on the California Coast Range, Tamvatnei deposit on the Chukchi Peninsula, etc. In areas of subaerial suprasubduction volcanism (Toscana type). Typical ore provinces are Toscana in Italy, Transcarpathia, Kamchatka, New Zealand, etc. In back-arc rifting zones (Nevada type). An example is the ore belt in the Basin and Range Province in the western USA with the Opalite, Cordero, and other deposits. 2. In orogenic belts. These Hg deposits are confined to regional thrusts related to strike-slip faults (Tien Shan type). Typical examples are the Khaidarkan, Chauvai, Chonkoi (Ulug-Too), and other deposits in Kirghizia and the Aktash and Chagan-Uzun deposits in Gorny Altai. 3. In zones of continental rifts and paleorifts (aulacogens), which are still of high tectonic and magmatic activity (Donetsk type). An example is the Donetsk Basin ore province with the Nikitovka and other Hg deposits. 4. In areas of within-plate rifting related to mantle plumes (Almaden type). Such deposits occur in the Iberian (Almaden, El Entridicho, Las Cuevas, etc.) and South Chinese (Wan Shan) provinces. Though Hg deposits formed in different geodynamic settings, this process was related to the development of similar-type secondary-hydrothermal and mixed-fluid systems [Borisenko, 1999]. Each ore-forming system is characterized by specific composition of hydrothermal solutions (determined by the paleohydrogeologic setting of its evolution) and different gradients of change in physicochemical parameters: temperature, pressure, and composition and concentration of solutions, which determine their acidityalkalinity (pH) and redox potential (Eh). These parameters govern the form of transfer and conditions of deposition of ore-forming components at geochemical barriers. The composition and concentration of hydrothermal solutions determine their possible metal-bearing capacity and ore potential. The existing concepts of the composition and concentration of mineral-forming solutions at Hg deposits rest upon the studies of modern thermal springs depositing Hg minerals, mainly detailed examinations of fluid inclusions in minerals of ores from Hg deposits (Fig. 1) [Obolensky et al., 1979; Obolensky and Borisenko, 1979]. Mineral-forming solutions are of diverse compositions and can be subdivided into three major groups according to the predominance of dissolved components: (1) sulfide-chloride (with and without CO2), (2) sulfide-bicarbonate-chloride, and (3) sulfide-carbonate solutions. For model computations, we chose solutions of each group (Table 1). The most specific feature of Hg-bearing hydrothermal solutions is their polygenous nature and mantle sources of Hg, which is confirmed by the presence of mantle 3He in them (Table 2) and the change in 3He/4He during the ore formation [Naumov et al., 2004]. Along with the composition and concentration of hydrothermal solutions that formed Hg deposits, modeling of ore formation processes requires knowledge of their metal-bearing capacity and ore potential [Belevantsev et al., 1982]. Based on the generalized and supplemented available literature data on the mercury solubility in aqueous electrolyte solutions in the system HgH2OH2SClCO2 at 25250 C, pH = 112, and different concentrations of complexing ligands (HS, S2, Cl), we performed computer modeling in order to estimate the possible metal-bearing capacities and ore potentials of different types of hydrothermal ore-forming solutions at Hg deposits (Table 3). The metal-bearing capacity was evaluated with regard to the presence of two Hg species, Hg(II) and Hg(0) (we used the refined constants of water solubility of Hg [Gushchina et al., 1989] and the transition Hg(II) Hg0 at high temperatures [Gushchina et al., 1990]), and mercury chloride complexes [Gushchina et al., aq 1994]. The presented data show strong temperature, CCl, and CS2 dependences of the Hg-bearing capacity of hydrotherms. We have also established an important role of Hg0 in mercury transfer in low-chloride and low-sulfide aq solutions. Computing modeling has shown that some types of hydrothermal solutions can transfer and deposit large amounts of Hg. For example, the Hg-bearing capacity of sulfide-chloride-CO2 and sulfide-carbonate solutions can reach 0.41.3 g/kg H2O (Table 3). Note that at high temperatures, mercury is transported with fluids mainly as Hg(0). Our studies confirmed the assumption on the prevailing participation of concentrated high-Hg ore-forming solutions in the formation of large and, especially, unique Hg deposits (Fig. 2, Table 4). The mechanism of Hg transfer, factors determining concentration of Hg-ores in some types of ore-forming systems, and amounts of these ores were studied using the Chiller program (Solveq) [Reed, 1982] and enclosed Soltherm-98 thermodynamic database supplemented with earlier obtained thermodynamic parameters of mixed Hg(II) complexes [Belevantsev et al., 1982] and Sb(III) chlorine complexes and monosulfide [Belevantsev et al., 1998a,b; Obolenskiy and Gushchina, 1999; Gushchina et al., 2000] and based on the SUPCRT92 thermodynamic database [Johnson et al., 1992]. The program permits computation of equilibria in high-concentration solutions. The concentrations of components in the initial aqueous solutions were calculated in mole/kg H2O. The redox potentials of the model solutions were specified based on the sulfidesulfate equilibrium (Table 5). 1319

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Fig. 1. Composition of solutions of gas-liquid inclusions in minerals of Hg, Sb, and As ores. Solutions: I NaClCaCl2; II NaClCO2; III NaHCO3NaCl; IV Na2CO3NaCl. Deposits: 1 Hg (with Hg-containing sulfosalts); 2 Sb and Sb-Hg deposits; 3 As and As-Hg: 1 Chazadyr, 2 Slavyanka, 3 Terligkhai, 4 Arzak, 5 Torasair, 6 Kurumdu-Aira, 7 Dzhylkydal, 8 Tyute, 9 Gorkhon, 10 Kadyrel, 11 Uzunsair, 12 Izerlig, 13 Tebek, 14 Aktash (Hg), 15 Chagan-Uzun, 16 Kurai, 17 Aktyul, 18 Cheremshanka, 19 Galkhaya, 20 Karasu, 21 Wan Shan, 22 Palyan, 23 Nikitovka, 24 Dzhizhikrut, 25 Barun-Shiveya, 26 Ust-Ege, 27 Khaidarkan, 28 Kadamzhai, 29 Tyrgetui, 30 Sarasa, 31 Aktash (As-Hg), 32 Lukhum, 33 Minkyule, 34 Elbrus, 35 Kodis-Dzeri, 36 Uzon, 37 Aktash (As), 38 Almaden, 39 Las Cuevas [Borisenko et al., 1974; Obolensky et al., 1979; Higueras et al., 2000].

We have constructed four main thermodynamic models of the possible mechanisms of mercury transfer and deposition in the form of cinnabar (-HgS) for ore-forming solutions of different compositions: (1) simple cooling (cooling only), for recent thermal springs, (2) mixing of high-chloride hydrothermal solutions with cold hydrosulfuric waters (mixing model), for telethermal deposits, (3) isoenthalpic boiling (P = f (T)), and (4) solutionrock interaction (rock titration model). ORE FORMATION IN MODERN THERMAL SOURCES Systems of modern thermal springs are localized in subaerial-volcanism areas on active continental margins and island arcs. Examples are the Wilbur Springs, Sulfur Bank, Sulfur Springs in California, Apapel and Uzon on the Kamchatka Peninsula, Ngawha, Blue Pool, and Acid Springs in New Zealand [Shikina et al., 1982; Davey and van Moert, 1986; Karpov, 1988; Sorokin et al., 1988; Chudaev et al., 2000; Giggenboch et al., 2003]. As these are real hydrothermal ore-forming systems which can serve as a prototype of paleohydrothermal systems, it is important to recognize equilibrium Hg, Sb, and As species in them and elucidate some regularities of sulfide mineral formation in the system H2OClH2SSbHgAs. For modeling ore formation processes in thermal-spring systems, we used the cooling model [Gushchina et al., 2004]. The considered thermodynamic models are based on the physicochemical parameters and chemical composition of thermal waters (Table 6). But for the systems to be electrically neutral, the concentrations of prevailing Cl, SO2, and Na+ in the solutions were changed to obtain equivalent concentrations of cations and 4 anions. 1320

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Table 1 Chemical Composition of Solutions for Thermodynamic Modeling Group no. 1 2 3 Composition of solution NaCl CaCl2 NaCl CO2 NaCl NaHCO3 NaCl Na2CO3 Concentration of main components (mole/kg H2O) 2.1 1.4 0.9 0.5 0.9 0.6 4.9 0.9 0.9 6.3 0.9 1.5 3.6 3.2 8.5 8.3 CH S = 101
2

[Cl]

(ionic strength)

pH at 25 C

Note

CH S = 101
2

CH S = 101 CH S = 104
2 2

1.7 0.5

1.7

3.1

12.2 11.5

CH S = 101 CH S = 104
2 2

Table 2
3

He/ 4He Values in Ore-Forming Fluids from Hg Deposits

3

Deposit Nikitovka (Ukraine) Khaidarkan (Kirghizia) Wan Shan (China) Aktash (Altai) Dzhikidal (Altai) Sulfur Bank1 (USA) Uzon2 (Kamchatka) New Zealand3 Steamboat Springs1 (USA)

He/ 4He106 0.12 0.06 0.38 0.28 1.6] 19.419.9 611.3 3.17.4 1.488.36

Note. 1 after [Torgersen and Jenkins, 1981]; 2 after [Rozhkov, 1979]; 3 after [Torgersen et al., 1982].

Table 3 Possible Metal-Bearing Capacity of Hydrotherms (from CHg at 250 C) Composition of solution (mole/kg H2O) 1 2 3 4 NaCl CaCl2 NaCl CO2 NaCl NaHCO3 NaCl Na2CO3 4.9 0.9 0.9 1.7 6.3 0.9 1.5 3.1 3 3 8 11 [Cl] (ionic strength)
0 pH250 C

Possible content of Hg (g/kg H2O) CH S = 101 (a)

2

Group no.

CH S = 104 (b)
2

5103 7104 3103 0.3

0.4 0.05 0.05 1.3

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Fig. 2. Hg content in ore-forming solutions of deposits (1) and thermal springs (2) with different Hg reserves.

The gas phase of the Wilbur Springs, Sulfur Bank (California), Ngawha, Blue Pool, Acid Springs (New Zealand), and hot Apapel spring waters is composed of CO2 and CH4, and the mineral phase, of quartz and cinnabar. The mineral phase of the Uzon caldera hydrotherm (Kamchatka) also contains orpiment and antimonite. The results obtained are listed in Fig. 3. Note that the waters of all considered thermal springs contain mercury as Hg0 . Its concentration reaches aq 5104 mole/kg H2O in the Blue Pool and Acid Springs acid waters at 250 C. This species is also predominant in H2S-free waters of these and the Apapel springs at low temperatures. Solutions rich in sulfides at temperatures of up to 150 C are dominated by HgSHS, which produces cinnabar by the reaction HgSHS = -HgSsol + HS . aq aq (1)

In the Uzon caldera hydrotherms, arsenic is present as HAsO2 and H2AsO hydrocomplexes, which produce 3 arsenic sulfide: 2HAsO2aq + 3H2Saq = As2S3sol + 4H2O. Antimony is present in the hydrotherms as Sb(OH)3aq and forms antimonite following the reaction (2)

Table 4 Contents of Hg in Ore-Forming Solutions at Some Deposits [Borisenko, 1999] Deposit Almaden (Spain) Idria (Slovenia) Nikitovka (Ukraine) Wan Shan (China) Thom, C 210140 200190 180 190115 Csol, wt.% <1.0 <1.5 5.2 (46) 6.518.0 Main component
Cl Na (Ca, Mg) Cl Na Ca

Hg concentration*, g/kg H2O 0.026 71043103 (17)104 (17)104

* Computed using inclusions with Hg liq.

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Table 5 Equilibrium Concentrations (mole/kg H2O) of Components in Initial Model Solutions Concentration in solution at 250 C Component I pH = 5.4 HS SO2 4 Na+ Cl Hg2+ HCO 3 K+ Fe
2+

Concentration in solution at 150 C V 4.6 1.00102 1.00104 1.70 1.70 1.12104 1.28102 1.00103 5.92103 4.11103 1.00103 1.00104 2.00 4.15 1.00104 9.54103 1.00101 1.00102 1.00103 1.00102 1.00102 1.00104 1.00102 1.00104 1.00 VI a 4.7 1.00104 1.00105 1.00105 VI b VII 8.4 1.00102 1.00105 2.00101 7.52101 4.00104 1.55101 1.00102 1.00103 1.00101 1.00102 2.00101 1.00104 1.00104 7.00102

II 7.3 1.00101 1.00105 9.00101 9.00101 4.09104 2.78102 1.131010

III 7.3 1.00102 1.00105 1.70 1.70 8.73104 3.60102

IV 5.5 1.00101 1.00105 9.00101 1.00 2.65104 5.37103 1.00102 5.96103 4.10102

1.00104 1.00104 3.60 4.40 1.15103 2.03102 8.00101

SiO2aq Sb(OH)3 Al
3+ 2+

Mg Ba

TiO2
2+

Mn2+ Ca2+

Sb(OH)3aq + 1.5H2Saq = 0.5Sb2S3sol + 3H2O.

(3)

At high temperatures, Sb can be transported as SbS and HSb2S, which form when the concentration of 2 4 dissolved H2S in the hot fluids increases. Near-neutral hydrotherms usually lack mercury chloride complexes though contain Cl (Table 5), but acid brines (Blue Pool and Acid Springs) are characterized by the formation of Hg(II) chloride complexes at high temperatures (>200 C) (Fig. 3). Thus, mercury is transported with modern thermal springs as Hg0 , whose content increases with temperature, aq and HgSHS, which exists in hydrosulfuric waters at < 200 C. The main factors responsible for cinnabar deposition from waters are their cooling and decrease in sulfide sulfur concentration. Since Sb and As are transported with hydrotherms mainly as HAsO2aq and Sb(OH)3aq, the deposition of their sulfides, in contrast to mercury sulfide, requires not only a temperature decrease but also the presence of dissolved H2S. Thermodynamic modeling showed that simple cooling of solutions compositionally similar to the Apapel, Blue Pool, and Acid Springs waters can result in the deposition of quartz, calcite, and magnesite but not cinnabar. Since the concentration of Hg0 does not reach its saturation limit (pK50 C = 5.76), Hgliq is not deposited. But aq Sorokin et al. [1988] notes that mercury sulfide can sometimes be produced through local concentration of sulfide sulfur. The model solutions compositionally similar to the Sulfur Bank, Wilbur Springs, and Ngawha waters containing sulfide sulfur deposit the same minerals and cinnabar (-HgS) when cooling from 250 to 100 C. The solution compositionally close to the Sb,As,Hg-containing Uzon hydrotherms deposits quartz, Ca and Mg carbonates, and antimonite (Sb2S3) when cooling from 250 to 150 C; on subsequent cooling to 100 C and below, orpiment (As2S3) and cinnabar are produced. Thus, the joint transfer of Sb and As in the form of hydroxyl complexes (Sb(OH)3, HAsO2, H2AsO) and 3 1323

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Table 6 Characteristics and Chemical Composition of Modern Thermal Spring Waters Concentration, mole/kg H2O103 NH+ 4 K 0.59 11.8 1.6 1.62 1.8 16.3 0.82 0.38 0.60 2.0 1.97 0.62 0.54 0.80 1.77 1.15 2.91 1.52 1.53 0.19 0.08 0.29 0.26 1.530 0.01 4.92 5.1 4.20 51.8 49.5 8.10 13.4 0.08 6.65 0.60 0.006 0.55 0.89 0.15 8.17 1.1 25.2 0.17 0.02 1.30 5.71 4.10 4.93 0.53 1.49 2.40 2.55 0.01 0.01 3.30 3.11 8.63 3.28 0.02 2.15 1.9 0.20 0.58 3.0 1.0 0.10 35 35.2 38.3 3.6 3.61 0.17 5.57 5.57 4.84 0.18 0.176 0.18 0.002 0.002 <105 0.04 4.9 2.4 310 0.24 121 5.20 11.0 4.98 0.5 0.17 0.03 0.03 0.5 0.7 2.3 18.2 6.2 53.9 0.35 1.00 2.7
+

mole/kg H2O107 References HCO 3 H2S Hg As Sb Shikina et al., 1982; Karpov, 1988

Spring Ca
2+

pH T, C at 20 C Na+ SiO2 Al
3+

Mg

2+

Cl

SO2 4

Sulfur Bank (California) 7.2 6.4 6.4 7.6 1.4 1.3 8.2 8.0 7.7 6.6 6.4 5.8 6.6 6.6 12.7 10.8 0.4 36.0 46.9 0.6 18.7 17 21.7 0.26 14.7 6.7 6.1 36.0 36.1 35.6 8.2 8.2 398 16.8

69

6.8

51.8

25.7

Wilbur Springs (California)

57

Ngawha (New Zealand)

48 48 98

1324

Shikina et al., 1982; Karpov, 1988; Davey and van Moort, 1986 Giggenbach et al., 2003 0.2 28 0.6 Karpov, 1988; 1.1 Sorokin et al., 1988 0.04 <105 0.08 0.108 0.19 0.07 0.15 267 270 Shikina et al., 1982; Karpov, 1988 6.56 Karpov, 1988; 23.8 Chudaev et al., 2000 1.06

Acid Springs, Blue Pool (White Island, New Zealand)

79 93

Upper Apapel (Kamchatka)

97 95

Lower Apapel (Kamchatka)

61 71

Tsentralny (Uzon caldera, Kamchatka)

90 90

Burlyashchy (Uzon caldera, Kamchatka)

91 90

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Fig. 3. Temperature dependences of the equilibrium concentrations of prevailing Hg species (mole/kg H2O) in various thermal springs.

Hg in the form of Hg0 passing into HgSHS complex takes place even at low temperatures (150 C and below), aq up to the formation of Sb, As, and Hg sulfides. To elucidate the possibility of Hg transfer with gas phase, we estimated the behavior of Hg in these solutions at high temperatures based on the isoenthalpic-boiling model (P = f(T)). We have established that the Ngawha fluid can transfer Hg in the form of Hg0 , which accumulates in the gas phase (up to 90% of its total content in aq the solution) as a result of the transition of Hg(II) sulfides and Hg0 into this phase. The same was earlier observed aq by Davey and van Moort [1986]. ORE FORMATION INVOLVING CHLORIDE SOLUTIONS Analysis of the available data on Hg contents in different types of natural waters shows that they are the highest in exogenous chloride brines, oil waters of some artesian basins, and petroleum pools rather than in volcanic gases and solutions of modern thermal springs in active-volcanism areas [Ozerova, 1986; Borisenko, 1999]. These high concentrations are typical of only artesian basins and petroleum structures localized beneath large faults. For example, chloride brines of the Danakil depression (East African Rift) contain up to 10 ppm Hg; oil and oil waters of the Cymric ore field (San Andreas Fault), 20.0 and 0.41 mg/l, respectively; etc. According to Ozerova [1986], the content of Hg in some gas pools in Central Europe reaches its saturation limit (>3 mg/m3); therefore, Hg is deposited as native mercury and amalgams in oil strings and in the form of cinnabar on oil-water pumpage at the Cymric deposit. High contents of Hg were found in artesian waters of the Ciscaucasian and Ciscarpathian basins. Such exogenous waters and gases with high Hg contents close to those of ore-forming solutions of Hg deposits are produced as a result of the metal supply with mantle gas flows [Ozerova, 1986; Borisenko, 1999]. Experimental studies and thermodynamic calculations [Belevantsev et al., 1982, 2004] showed that acid (pH = 3.55) chloride brines of haloid deposits are of the highest Hg-bearing capacity. At 200 C (upper limit of H2S formation in Hg-ores (data of fluid inclusion studies)), they can dissolve up to 0.n g/l Hg. Chloride brines of this kind were revealed in the Danakil depression (East African Rift) and Cymric oil field (California). Mercury can accumulate not only in exogenous waters but also as dry gas pools beneath corresponding 1325

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screens. It occurs in great amounts (up to 3 mg/m3 and more, up to its saturation limit) at some European gas deposits localized above large transcontinental faults [Ozerova, 1986]. The saturation limit of mercury in those gases is determined by the temperature at which it is concentrated: 0.02 mg/m3 at 250 C, 23.3 at 100 C, and 115.5 at 200 C. This testifies to the formation of secondary reservoirs of Hg-bearing solutions and gases in such exogenous settings, where thereafter secondary hydrothermal ore-forming systems producing Hg deposits originate. Mercury contents in exogenous waters are commensurate with those in rock-forming solutions of Hg deposits, and Hg reserves in some gas pools are estimated at 30005000 tons, i.e., close to those in medium-sized Hg deposits. Thus, there are two types of natural exogenous-water and gas settings of mercury accumulation: (1) artesian chloride-brine basins in synclinal structures (troughs, depressions, grabens) and (2) petroleum pools with gas Hg and associated exogenous waters in anticlinal structures. These settings determine two main structural positions of Hg deposit localization: (1) periphery of synclinal structures where paleoartesian chloride-brine basins existed (deposits in the Tuva and Minusa basins, Slovak ore mountains, Pfalz in Germany, etc.) and (2) anticlinal structures (anticlines, brachyanticlines, dome-shaped uplifts of thrust structure surface, etc.) (cinnabar and antimonite-cinnabar deposits in the Donetsk Basin and Tien Shan, Monte Amiata, Idria, etc.) The following evolution of ore-forming systems localized in artesian chloride-brine basins proceeded by the scheme: destruction of artesian basins formation of artesian-water discharge structures mixing of thermodynamically nonequilibrium waters from different hydrodynamic levels (deeply localized reduced metalbearing (HgSbAs, Ba, Sr, Cu, Pb, Zn) brines and sulfurous or sulfate waters of upper horizons) ore deposition. This model of Hg-ore formation is correctly described by the thermodynamic solutions mixing model. The results of computer modeling (Fig. 4) show that in weak-acid (pH 5) low-(1m) and high-(4.4m)chloride solutions with low concentrations of sulfide sulfur (0.0001m) (solution I, Table 5), prevailing forms of mercury transfer at high temperatures (250150 C) are chloride complexes HgCl2 n. At the same time, Hg0 reached an n aq equilibrium with Hgliq; therefore, native mercury was deposited throughout the solution cooling. Since cinnabar was not deposited from this solution at such low concentrations of sulfide sulfur, we applied a model of mixing of metal-bearing and cold hydrosulfuric (0.001m) solutions. This led to an increase in the content of sulfide sulfur in the solution under study. The subsequent cooling of the solution resulted in cinnabar deposition (the mineral was produced mainly from HgCl2, HgCl, and HgCl2) following the reaction 4 3 HgCl2 + H2Saq -HgSsol + 2H+ + 4Cl . aq 4aq aq (4)

The solutions mixing model describes the most productive mineral formation process: Chloride solutions can keep high contents of dissolved mercury and deposit cinnabar under appropriate conditions. This model of ore formation process is typical of many Hg deposits formed through the mixing of high-temperature Hg-bearing chloride solutions with cold hydrosulfuric waters. Thus, chloride complexes play an important role in the transfer of Hg(II) and other metals by these solutions, particularly when the latter are poor in sulfide sulfur [Naumov et al., 2002; Belevantsev et al., 2004; Pavlova et al., 2004; Borisenko et al., 2006a]. Cinnabar deposition during the cooling of the solution is due to the increasing content of sulfide sulfur as a result of the solution mixing with cold hydrosufuric waters or metasomatic replacement of the sulfide-enriched host rocks.

Fig. 4. Concentration of Hg in sulfide-chloride solution (I) with CHS = 0.0001 mole/l (Table 5) depending on pH and temperature (cooling model a) and pH at T = 110 C (mixing model b). Bold lines mark produced solid phase (-HgS, Hgliq). 1326

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Fig. 5. Concentration of Hg in NaHCO3NaCl solution with CHS = 0.1 mole/l (solution II) and NaCO3NaCl solution with CHS = 0.01 mole/l (solution III) depending on pH and temperature (250110 C (isoenthalpic model, P = f (T); 11090 C (cooling model, P = 1 bar); and 90 C and below (condensation)). Concentrations of Sb and Hg in NaHCO3NaCl solutions with CHS = 0.1 mole/l (solution IV) and CHS = 0.01 mole/l (solution V) depending on pH and temperature (250110 C (isoenthalpic model, P = f (T); 11090 C (mixing model); and 90 C and below (condensation)).

For the case when ore-forming systems discharge in fractured structures, we used the isoenthalpic boiling model (P = f(T)). Based on this model, we estimated the behavior of Hg in NaHCO3NaCl (II, Table 5) and Na2CO3NaCl (III) solutions (Fig. 5). Since the solutions are near-neutral or alkaline, they transfer mercury in the form of HgS2, HgSHS, and Hg0 . As the solution (T = 250 C) reaches the gas saturation pressure, it boils up 2 aq to produce gas phase (CO2, CH4, H2S, N2, etc.) containing Hggas (Table 7). Gas mercury accumulates in the gas phase as a result of the transition of dissolved Hg(II) species and Hg0 from the solution. Subsequent cooling of aq the solution along the two-phase equilibrium PT-curve leads to a change in its pH and cinnabar deposition (the mineral is produced mainly from HgSHS) following the reaction HgSHS = -HgSsol + HS . aq aq (5)

Aftercooling of the residual solutions still saturated with mercury (in the form of HgS2) and condensation 2 of the gas phase lead to the formation of cinnabar by the reactions HgS2 + H+ = -HgSsol + HS , 2aq aq aq Hggas + H2Saq = -HgSsol + H2gas. (6) (7)

As seen from Table 7 and Fig. 5, the gas phase resulted from the isoenthalpic boiling of the NaHCO3NaCl solution (II) is less saturated with CO2 and Hggas (the latter amounts to 42% of the total Hg content in the initial solution) than that produced from the Na2CO3NaCl solution (III) (up to 81% Hggas). Solution II is more alkaline and contains an order of magnitude more sulfide sulfur than solution III, which ensures a more intense formation of complex HgS2 and its higher stability in the solution (Fig. 5). Thus, this model takes into account the mutually 2 related changes in two main physicochemical parameters of ore deposition, temperature and pressure, in zone of intense ore formation at most Hg deposits and therefore best reflects this process than the other models. In the context of the considered models, we estimated the joint transfer and deposition of Hg and Sb sulfides in NaCl solutions. Modeling of ore formation at Sb-Hg deposits was carried out for weakly mineralized (up to 10%) 1327

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Table 7 Changes in Concentrations (lgm) of Some Components in Solutions II, III, IV, and V and Corresponding Gas Phases with Decreasing Temperature (from 250 to 110 C) and Pressure (Isoenthalpic Boiling Model (P = f (T)) Pressure, bars Component 39.71 Solution II CO2 CH4 H2 H2S Hg 2.14 4.03 4.02 2.34 3.61 5.37 6.47 6.44 4.28 3.67 Gas II 4.67 5.93 5.79 5.15 6.23 2.23 2.29 2.23 1.65 3.77 38.41 Solution III 2.09 5.13 4.36 3.50 3.76 4.86 7.07 6.77 5.22 4.15 Gas III 4.61 6.96 6.05 6.23 5.83 1.80 2.81 2.48 2.51 3.15 40.51 Solution IV 2.54 2.62 3.57 2.00 3.60 5.45 7.05 6.56 4.43 6.71 Gas IV 5.07 4.52 5.34 4.80 6.17 2.40 2.87 2.35 1.79 3.75 39.01 Solution V 1.90 3.58 4.02 2.79 3.96 4.95 8.93 7.21 5.43 7.19 Gas V 4.42 1.89 5.41 4.67 5.71 2.92 5.53 2.71 6.02 3.955

NaHCO3NaCl sulfide solutions (Table 5, IV and V) typical of such deposits. Their gas phase was composed of CO2 and CH4, and their mineral phase, of quartz, antimonite, and cinnabar (Fig. 5). The main factor responsible for the joint deposition of antimonite and cinnabar from weakly mineralized NaHCO3NaCl hydrothermal solutions is a decrease in pH at <180 C. Using the mixing model provides a decrease in pH, whereas simple solution cooling does not significantly change it. Mixing of the hydrothermal solution with cold (25 C) acid (pH = 5) meteoric water results in a decrease in its temperature and pH (to 4.8) and the deposition of Hg and Sb sulfides following reactions (5) and (8): SbS + 0.5H2O = 0.5Sb2S3sol + 0.5HS + 0.5OH . 2aq aq aq (8)

Parageneses bearing only antimony are produced from weakly mineralized Sb,Hg-containing hydrothermal NaHCO3 sulfide solutions on isoenthalpic boiling (P = f (T)). The Hg transport with the gas phase (CO2, H2S, CH4) and the condensation of the latter under hydrothermal conditions ensure separate deposition of cinnabar and antimonite. Mercury accumulates in the gas phase as a result of the transition of soluble Hg(II) species and Hg0 from the solution. Subsequent cooling of the solution to 110 C leads to an increase in its pH from 5.5 to aq 7.3 (release of CO2 and H2S as a gas phase on the background of pressure drop) and a higher stability of SbS 2 and HgS2 complexes in the alkaline medium. Condensation of the cooling gas phase (Hggas and H2Sgas) also 2 results in cinnabar deposition (reaction (7)). Note that the mechanism of isoenthalpic boiling also acts in model solutions with lower concentrations of sulfide sulfur, but a prevailing form of Sb transfer in them is Sb(OH)3 rather than sulfide complexes (Fig. 5). It is this complex that gives rise to antimonite (reaction (3)). Moreover, the modeling showed a drastic decrease in pH (from 7.3 to 5.5 and 4.6) and concentration of Hg (1.57.5 times) of the Hg-Sb-solutions as compared with the system HgH2SClH2OCO2. The drop in pH of the Sb-saturated solutions in this system is, most likely, responsible for the decrease in their Hg content because of the significant decrease in the concentrations of complexes HgS2 and HgSHS, which become less stable in the acid medium 2 (Fig. 5). The gas phases produced on the isoenthalpic boiling of the Hg-Sb-solutions are more saturated with CO2 and Hggas (up to 6799% Hg of its total concentration in the initial solution) than those produced from similar Hg-solutions (4281% Hg) (Tables 5 and 7). COMPUTER MODELING OF THE INTERACTION OF HYDROTHERMAL SOLUTIONS WITH THE HOST ROCKS At many Hg deposits, ore formation is accompanied by the formation of aureoles of metasomatic wallrocks resulting from the interaction of the host rocks with hydrothermal solutions. Metasomatites of argillizite and listwaenite formations are the most typical; they develop after aluminosilicate rocks of acid and basic compositions, respectively. We performed modeling of the solutionrock interaction by the example of the comprehensively studied Terligkhaya (Tuva) and Chagan-Uzun (Gorny Altai) Hg deposits [Kuznetsov et al., 1970; Obolensky, 1985]. 1328

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This process was modeled only for nonmetallic mineral assemblage at the Chagan-Uzun Hg deposit using the Chiller (Rock titration) [Reed, 1998] and Selektor [Karpov et al., 1997] computer programs. The modeling was carried out by the flow reactor method, which implies that a change in the system composition is a function of the water/rock ratio (i.e., the ratio of the total amount of initial solution to the total amount of reacted rock). Argillization and ore deposition. The peculiarities of acid-rock argillization were considered by the example of the hydrothermal alteration of andesite-dacitic porphyrite of the Terligkhaya Hg deposit (Tuva) (Table 8). Modeling of the composition of infiltration column was performed using solutions with different concentrations of sulfide sulfur (Table 5) and varying water/rock ratio (w/r) at 150 C (Fig. 6, a, b). During the interaction of initial acid (pH = 4.7) high-chloride (4.2m) solutions rich in sulfide sulfur (0.0001m VI a) and (0.001m VI b) with andesite-dacitic porphyrite, we observed periodical deposition and dissolution of cinnabar (-HgSsol) and metallic mercury (Hgliq) depending on the flow rate of fresh portions of hydrothermal high-chloride solutions and increase in pH from 1.9 to 5.4 on the complete dissolution of kaolinite and deposition of Fe chlorites. Under the interaction of hydrothermal solution VI a with rock at 150 C, cinnabar is produced mainly from mercury chloride complexes (HgCl2, HgCl, and HgCl2), and under the similar interaction of solution VI b, 3 4 cinnabar results from the decomposition of Hg(HS)2: HgCl4aq2 + H2Saq -HgSsol + 2H+ + 4Cl , aq aq (9)

(10) Hg(HS)2aq = -HgSsol + H2Saq. 0 , whose concentration reaches the value at which Native mercury is deposited from these solutions as Hgaq it is in equilibrium with Hgliq (K150 C = 1.6 105). In our earlier experimental studies of the role of dissolved Hg0 in the mercury transfer with natural hydrotherms [Gushchina et al., 1990, 1994] we showed the possibility aq of determining its high concentrations in hot chloride-sulfide solutions. The interaction of these solutions with

Table 8 Results of Chemical Analyses of Fresh and Altered Host Rocks from Some Mercury Deposits [Kuznetsov et al., 1978] Rock, deposit Unaltered andesite-dacitic porphyrite (Teligkhaya) Argillized porphyrite Hydromica zone Argillized porphyrite Kaolinite zone Argillized porphyrite Quartz zone Unaltered serpentinite (Chagan-Uzun) Carbonate-talc rock Listwaenite Silicified dolomitized limestone SiO2 TiO2 Al2O3 Fe2O3 FeO 69.60 0.20 12.45 1.03 2.45 MgO MnO CaO Na2O K2O 0.11 3.76 2.12 1.96 LOI 5.47 H2O 0.40 Total (wt.%) 99.55

69.0

0.20 16.15

1.70

1.07

0.94

3.10

2.01

5.02

0.70

99.89

58.00 0.40 26.20

0.82

0.31

0.94

0.20

2.24 10.00 1.40 100.52

81.80 0.20 10.85

0.47

0.61

0.20

0.67

4.57

0.60

99.97

33.82 0.48

3.58

6.48

2.82 35.40 0.22

2.57

15.35

100.72

26.54 0.07 22.57 0.04 26.39 0.06

1.62 1.16 1.26

8.12 5.84 7.31

1.94 29.74 0.19 10.03 2.88 29.66 0.10 3.76 4.23 0.10 24.29 4.43

0.07 0.12

21.34

99.59 100.08 99.34

0.10 33.90 0.13 31.02

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Fig. 6. Results of modeling of argillization of andesite-dacitic porphyrite of the Terligkhaya Hg deposit (Tuva) at 150 C (solutions VI a and b, Table 5) (a, b) and listwaenitization under the interaction of sulfide-chloride-carbon dioxide solution with serpentinite of the Chagan-Uzun Hg deposit at 150C (solution VII, Table 5) (c, d).

andesite-dacitic porphyrite when fresh portions of acid high-chloride waters (VI a) pass through the rock (up to 10 g) leads to the dissolution of cinnabar and formation of HgCl2 (by reaction (9)). Under the interaction 4 of the model solutions with the rock (10 to 1000 g and more), this mercury complex (solution VI a) and cinnabar are converted into Hg0 at high temperature (150 C) and drastic increase in pH of the solutions from 2 to 5.4 aq (during the complete dissolution of kaolinite and deposition of chlorites (daphnite and clinochlore)), which leads to the saturation of the mineral-forming solutions with Hg0 and deposition of Hgliq from them: aq HgCl2 + H2O = Hg0 + 0.5O2aq + 2H+ + 4Cl , 2aq aq aq aq -HgSsol + 4H2O = Hg0 + SO2 + 8H+ , aq 4aq aq Hg0 = Hgliq. aq (11) (12) (13)

Native metals in hot reduced solutions are more stable than their sulfides [Kolonin and Ptitsyn, 1974; Fein and William-Jones, 1997]. Note that the sequence of deposition of these minerals reflects an increase in the alkalinity of mineral-forming solutions during the hydrothermal process and a change in the chemical composition of porphyrites during their argillization [Kuznetsov et al., 1978; Borisenko and Grechishcheva, 1982]. The mole quantities of elements in the model solutions changed as the latter passed through the rock and interacted with it: The contents of Fe and Al drastically (by several orders of magnitude) decreased, those of K, Ca, and Ba also became lower, and the contents of Na and Si increased. The observed horizontal metasomatic zoning in the host rocks and the synchronous rock metasomatism and 1330

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ore deposition (deposition of cinnabar in particular zones of metasomatic columns) are confirmed by results of our thermodynamic modeling. The theoretical model column of acid leaching of andesite-dacitic porphyrite looks as follows: Qtz + Kaol + Pyr + Cin Qtz + Chl + Ser + Hgliq (Cin) Qtz + Mic + Chl + Zeol + Hgliq. Thus, cinnabar can occur as fine metasomatic dissemination in the inner zones of these columns if it was not completely converted into native mercury under the interaction of hydrothermal chloride-sulfide solution with unaltered porphyrites. Effective cinnabar deposition requires mixing of hot Hg-bearing high-chloride solution with cold hydrosulfuric waters (see the mixing model above). Listwaenitization and ore deposition. Of all known Hg deposits, the Chagan-Uzun one is the most favorable for thermodynamic modeling of the interaction of sulfide-chloride-carbon dioxide solutions with serpentinites [Obolensky and Borisenko, 1978; Kuznetsov et al., 1978]. Modeling of the composition of metasomatic column of hydrothermally altered serpentinites was performed using sulfide-chloride-carbon dioxide solution (VII) (Table 5) at 150 C. The results are given for a system with MgO : CaO : SiO2 = 2 : 1 : 1 (i.e., with some silica deficit) (Fig. 6, c, d). Under the interaction of initial CO2gas-bearing alkaline (pH = 8.4) sulfide-chloride fluid with unaltered serpentinite, the latter is partly converted into talc, the solution becomes neutral, and dolomite, magnesite, sericite, and quartz are deposited. Since the Hg-bearing solution is saturated with Hg0 , native mercury can also be deposited (by reaction (13)), which indicates aq that the solution is moderately reduced. The interaction of dissolved H2Saq with the host rocks results in the deposition of pyrite (FeS2) and subsequent decrease in pH of the solution to 4.5 and below, which favors the formation of kaolinite, pyrite, graphite, and cinnabar. The listwaenites in this zonal metasomatic columns host both pyrite and cinnabar. The alteration of serpentinite is accompanied by the intense supply of CO2 and Ca and partial removal of Mg [Kuznetsov et al., 1978]. Under the hydrothermal solutionserpentinite interaction, mercury is transferred in the form of sulfides (HgS2, HgSHS, and Hg(HS)2), and -HgSsol is deposited from the weakly 2 acid solution as a result of the decomposition of these complexes (reactions (5), (6), and (10)). CONCLUSIONS Study of the mineral compositions of ores, metasomatic wallrocks, and hydrothermal ore-bearing solutions that produced Hg deposits of different types gave insight into their formation processes in the systems HgH2OClH2SCO2 and HgSbH2OClH2SCO2 with varying physicochemical parameters. Waters of modern thermal springs lack mercury chlorides. At low temperatures, Hg is transferred in the form of HgSHS, and at high temperatures (>200 C), as Hg0 . In H2S-free waters, Hg0 remains the main Hg species aq aq even at low temperatures. We have established that fluids can transport mercury in the form of Hggas, which accumulates in the gas phase as a result of the transition of Hg(II) sulfides and Hg0 into the latter. Cinnabar is aq deposited from hydrotherms as the temperature drops and sulfide sulfur is concentrated. Since Sb and As are transported with hydrotherms mainly as complexes Sb(OH)3 and HAsO2, the deposition of their sulfides, in contrast to Hg sulfides, requires not only a temperature decrease but also the presence of dissolved H2S. In acid chloride solutions with low concentrations of S2, prevailing forms of mercury transfer at high temperatures are chloride complexes HgCl2n . On cooling, the solutions deposit cinnabar, which is caused by the n increase in their concentration of sulfide sulfur on their mixing with H2S-containing solutions or by the metasomatic replacement of the sulfide-enriched host rocks. In near-neutral or alkaline NaHCO3NaCl and Na2CO3NaCl solutions, mercury is transported in the form of sulfide complexes HgS2 and HgSHS and, partly, as Hg0 , and antimony is transferred as SbS or Sb(OH)3. 2 aq 2 The main factors responsible for the cinnabar deposition from these solutions are their cooling and decrease in their sulfide sulfur concentration; antimony sulfide deposition requires, in addition, a decrease in pH of the solution and the presence of dissolved H2S in it. Isoenthalpic boiling (P = f (T)) of the solutions and condensation of the cooling gas phase (Hggas and H2Sgas) also lead to cinnabar deposition. Thus, these types of solutions seem to play a leading role in the formation of most known hydrothermal mercury deposits because they are most widespread in natural hydrothermal systems and deposit concentrated ores. At the above-considered Hg deposits differing in the composition of ore-forming hydrothermal solutions, wallrock metasomatism develops in different ways. The deposits produced by sulfide-chloride solutions show weak pre-ore and intense syn-ore rock metasomatism. Ore deposition there completes syn-ore rock metasomatism. The deposits formed by sulfide-chloride-carbon dioxide solutions abound in both pre-ore and syn-ore metasomatites. First cinnabar generations are produced at the beginning of syn-ore metasomatism, whereas most of ores are deposited together with kaolinite (dickite) at its final stage. At the deposits produced by sulfide-bicarbonate-car1331

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bonate solutions, pre-ore metasomatites drastically dominate over syn-ore ones. Ore deposition there completes syn-ore metasomatism. The considered models of the formation of Hg deposits shed light on many moot points of their genesis, such as their spatial separation from other types of mineralization and magmatism manifestations, the high metal-bearing capacity and widely varying chemical composition of their ore-forming solutions (usually corresponding to the composition of particular exogenous waters), the mantle source of their Hg (Sb, As), and the supply of their S, Ba, Sr, Ni, Co, and Pb from the host rocks, as follows from the isotope-geochemical data. We have established that exogenous waters play an important role in the formation of Hg deposits as they are not only a medium for Hg accumulation but also a source of many elements (Ba, Sr, S, etc.) and serve as an effective geochemical barrier for ore deposition (H2S, SO2, O, etc.). In the geological context, their participation 2 in the ore formation is expressed as a paleohydrogeologic control of Hg mineralization at regional and local levels [Borisenko, 1990]. We thank Prof. M.Reed, Oregon University, USA, for kind provision of the Chiller program and Prof. V.I. Belevantsev for help in study of mercury solubility. This work was supported by grants 04-05-64485 and 04-05-64485 from the Russian Foundation for Basic Research, Scientific School grant 4933.2006.5, and grant DSP.2.1.1.702 from the Ministry for Russian Science and Education. REFERENCES Belevantsev, V.I., L.V. Gushchina, and A.A. Obolensky, Hydrothermal solutions and mercury migration, in Hydrothermal low-temperature ore formation and metasomatism [in Russian], 349, Nauka, Novosibirsk, 1982. Belevantsev, V.I., L.V. Gushchina, and A.A. Obolensky, Solubility of antimonite Sb2S3: examination of known interpretations and refinements, Geokhimiya, 1, 6572, 1998a. Belevantsev, V.I., L.V. Gushchina, and A.A. Obolensky, Antimony in hydrothermal solutions: analysis and generalization of data on Sb(III) chloro complexes, Geokhimiya, 10, 10331038, 1998b. Belevantsev, V.I., V.I. Malkova, L.V. Gushchina, and A.A. Obolensky, Equilibrium and electron spectra of Hg(II) chloro complexes in perchlorate-aqueous medium, Zhurnal Koordinatsionnoi Khimii, 30, 7, 499506, 2004. Borisenko, A.S., Paleohydrogeologic control of epithermal mineralization in the Altai-Sayan folded area, in Sources of ore matter and physicochemical conditions of epithermal ore formation [in Russian], 7484, Nauka, Novosibirsk, 1990. Borisenko, A.S., Ore-forming systems of hydrothermal low-temperature deposits (types of systems, genetic models, and ore production factors). Abstr. ScD thesis [in Russian], 97 pp., OIGGM SO RAN, Novosibirsk, 1999. Borisenko, A.S., and V.N. Grechishcheva, Formations of metasomatic wallrocks of Hg deposits in Tuva, in Hydrothermal low-temperature ore formation and metasomatism, 4382, Novosibirsk, 1982. Borisenko, A.S., E.A. Naumov, and A.A. Obolensky, Types of gold-mercury deposits and their formation conditions, Russian Geology and Geophysics (Geologiya i Geofizika), 47, 3, 342354 (342354), 2006. Borisenko A.S., A.A. Obolenskiy, and E.A. Naumov, Global tectonic setting and deep mantle control on Hg and Au-Hg deposits, in Mineral deposits research: Meeting the Global Challenge, Vol. 1, 36, Springer, Berlin, Heidelberg, New York, 2005. Borisenko, A.S., V.I. Sotnikov, A.E. Izokh, G.V. Polyakov, and A.A. Obolensky, Permo-Triassic mineralization in Asia and its relation to plume magmatism, Russian Geology and Geophysics (Geologiya i Geofizika), 47, 1, 170186 (166182), 2006. Borisenko, A.S., V.I. Vasilev, A.A. Obolensky, and N.A. Shugurova, Composition of gas-liquid inclusions in minerals of ores from Hg deposits and chemical composition of hydrotherms, Dokl. AN SSSR, 214, 4, 673676, 1974. Chudaev, O.V., V.A. Chudaeva, G.A. Karpov, U.M. Edmunds, and P. Shand, Geochemistry of waters in the main geothermal areas of Kamchatka [in Russian], 157 pp., Dalnauka, Vladivostok, 2000. Davey, H.A., and J.C. van Moort, Current mercury deposition at Ngawha Springs, New Zealand, Appl. Geochem., 1, 7593, 1986. Distanov, E.G., V.I. Sotnikov, A.A. Obolenskii, A.S. Borisenko, A.P. Berzina, and K.R. Kovalev, Main factors of formation of large and superlarge mineral deposits of crust-mantle ore-forming systems (by the example of Siberia), Geologiya i Geofizika (Russian Geology and Geophysics), 39, 7, 870881 (879888), 1998. Fein, J.B., and A.E. William-Jones, The role of mercury-organic interactions in the hydrothermal transport of mercury, Econ. Geol., 92, 2028, 1997. Giggenbach, W.F., H. Shinohara, M. Kusakabe, and T. Ohba, Formation of volcanic brines through interaction 1332

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of magmatic gases, seawater, and rock within the White Island volcanic-hydrothermal system, New Zealand, in Special Publications of the Society of Economic Geologists, eds. S. Simmons and I. Graham, 10, 1940, 2003. Gushchina, L.V., V.I. Belevantsev, G.R. Kolonin, and A.A. Obolensky, The role of dissolved Hg0 in natural aq hydrotherms, in Sources of ore matter and physicochemical conditions of epithermal ore formation [in Russian], 113123, Nauka, Novosibirsk, 1990. Gushchina, L.V., V.I. Belevantsev, and A.A. Obolensky, Determination of Hgliq solubility in water by high-temperature spectrophotometry, Geokhimiya, 2, 274281, 1989. Gushchina, L.V., V.I. Belevantsev, and A.A. Obolenskiy, Hg0 in mercury transport by hydrothermal aq solutions, Geochem. Intern., 31, 1, 9399, 1994. Gushchina, L.V., A.A. Borovikov, and A.P. Shebanin, Raman spectroscopic experimental study of Sb(III) complex formation in alkaline sulfide solutions at high temperatures, Geokhimiya, 5, 565568, 2000. Gushchina, L.V., A.A. Obolenskiy, and E.A. Naumov, Mercury mineralization in modern hydrothermal systems: computer modeling of ore-forming processes, in Metallogeny of the Pacific Northwest: tectonics, magmatism and metallogeny of active continental margins. Proc. Interim IAGOD conf., 634637, Dalnauka, Vladivostok, 2004. Higueras, P., R. Oyarzum, J. Munha, and D. Morata, The Almaden metallogenic cluster (Ciudad Real, Spain): alkaline magmatism leading to mineralization process at an intraplate tectonic setting, Rev. Soc. Geol. Esp., 13, 1, 105119, 2000. Johnson, J.W., E.H. Oelkers, and H.C. Helgeson, SUPCRT92, a software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bars and 0 to 1000 C, Comput. Geosci., 18, 899947, 1992. Karpov, G.A., Modern hydrotherms and Hg-Sb-As mineralization [in Russian], 183 pp., Nauka, Moscow, 1988. Karpov, I.K., K.L. Chudnenko, and D.A. Kulik, Modeling chemical mass transfer in geochemical processes: thermodynamic relations, conditions of equilibrium and numerical algorithms, Amer. J. Sci., 297, 767806, 1997. Kolonin, G.R., and A.B. Ptitsyn, Thermodynamic analysis of conditions of hydrothermal ore formation [in Russian], 102 pp., Nauka, Novosibirsk, 1974. Kuznetsov, V.A., The Chagan-Uzun mercury deposit in Altai, Vestnik Zapadno-Sibirskogo Geologicheskogo Upravleniya, 5, 2636, 1934. Kuznetsov, V.A., The Pezas cinnabar deposit on the western slope of Kuznetsk Alatau, Vestnik Zapadno-Sibirskogo Geologicheskogo Upravleniya, 3, 1826, 1939. Kuznetsov, V.A., Geologic structure and mineral resources of the Taidon-Ters area on the western slope of Kuznetsk Alatau, in Materials on geology of West Siberia [in Russian], Tomsk, 10, 52, 1102, 1940. Kuznetsov, V.A., The West Siberian mercury-bearing province, Vestnik Zapadno-Sibirskogo Geologicheskogo Upravleniya, 5, 122, 1943. Kuznetsov, V.A., Regularities of the formation and spatial localization of mercury deposits in the Altai-Sayan folded area, in Regularities of mineral resource localization [in Russian], Vol. 1, 275288, Moscow, 1958. Kuznetsov, V.A., The Central Asian mercury belt, Geologiya i Geofizika (Soviet Geology and Geophysics), 15, 5, 103112 (8288), 1974. Kuznetsov, V.A., and A.S. Mukhin, New mercury deposit in Gorny Altai, Vestnik Zapadno-Sibirskogo Geologicheskogo Upravleniya, 1/2, 1622, 1936. Kuznetsov, V.A., and A.A. Obolensky, The questions of Hg-deposit genesis and the problem of sources of ore matter, Geologiya i Geofizika, 11, 4, 4456, 1970. Kuznetsov, V.A., A.A. Obolensky, and V.I. Vasilev, The experience of formation-based systematization of mercury deposits in Siberia and the Far East, in Endogenous ore associations in Siberia and the Far East [in Russian], 197202, Nauka, Moscow, 1966. Kuznetsov, V.A., V.I. Vasilev, A.A. Obolensky, and I.P. Shcherban, Geology and genesis of mercury deposits in the Altai-Sayan area [in Russian], 294 pp., Nauka, Novosibirsk, 1978. Naumov, E.A., A.A. Airiyants, A.S. Borisenko, A.A. Borovikov, I.L. Kamenskiy, and V.N. Reutskiy, Helium, carbon and oxygen isotope composition study of the epithermal deposits, in Metallogeny of the Pacific Northwest: tectonics, magmatism and metallogeny of active continental margins. Proc. Interim IAGOD conf., 300303, Dalnauka, Vladivostok, 2004. Naumov, E.A., A.A. Borovikov, A.S. Borisenko, M.V. Zadorozhnyi, and V.V. Murzin, Physicochemical conditions of formation of epithermal gold-mercury deposits, Geologiya i Geofizika (Russian Geology and Geophysics), 43, 12, 10551064 (10031013), 2002. 1333

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Obolensky, A.A., Genesis of deposits of Hg-ore association [in Russian], 193 pp., Nauka, Novosibirsk, 1985. Obolenskii, A.A., N.A. Berzin, E.G. Distanov, and V.I. Sotnikov, Metallogeny of the Central Asian orogenic belt, Geologiya i Geofizika (Russian Geology and Geophysics), 40, 11, 15881604 (15621576), 1999. Obolensky, A.A., and A.S. Borisenko, The correlation of listwaenitization and ore deposition at mercury deposits of magnesian-carbonate-cinnabar (listwaenite) type, in Geology and genesis of rare-metal and polymetallic deposits in Siberia [in Russian], 2742, Nauka, Novosibirsk, 1978. Obolensky, A.A., and A.S. Borisenko, Physicochemical parameters and main factors of ore formation at epithermal Hg, Sb, and As deposits, in Main parameters of natural processes of endogenous ore formation [in Russian], Vol. 2, 181193, Nauka, Novosibirsk, 1979. Obolensky, A.A., A.S. Borisenko, and R.V. Obolenskaya, The nature of hydrothermal solutions and sources of ore matter of epithermal Hg, Sb, and As deposits, in The nature of solutions and sources of ore-forming substances of endogenous deposits [in Russian], 4271, Nauka, Novosibirsk, 1979. Obolenskiy, A.A., and L.V. Gushchina, Antimony in hydrothermal solutions: forms of transfer, metal content, and conditions of stibnite deposition, in Mineral deposits: processes to processing, 129132, Balcema, Rotterdam, 1999. Obolenskiy, A.A., and E.A. Naumov, Global mercury belts and geodynamic position of ore-forming systems of mercury deposits, in Mineral exploration and sustainable development, 511515, Millpress, Rotterdam, 2003. Ozerova, N.A., Mercury and endogenous ore formation [in Russian], 231 pp., Nauka, Moscow, 1986. Pavlova, G.G., L.V. Gushchina, A.A. Borovikov, A.S. Borisenko, and A.A. Obolensky, Silver and antimony in hydrothermal solutions of Ag-Sb deposits, Geologiya i Geofizika (Russian Geology and Geophysics), 45, 10, 11861197 (11361148), 2004. Reed, H.M., Calculation of multicomponent chemical equilibria and reaction processes in systems involving minerals, gases and aqueous phase, Geochim. Cosmochim. Acta, 46, 513525, 1982. Reed, M.H., Calculation of simultaneous chemical equilibrium in aqueous-mineral-gas systems and application to modeling hydrothermal process, Techniques in hydrothermal ore deposits geology. Rev. Econ. Geol., 10, 109124, 1998. Rozhkov, A.M., Gas composition, Ra radioactivity, and 3He/4He ratio as an indicator of the conditions of ore deposition from thermal waters of the Uzon caldera (Kamchatka), Vulkanologiya i Seismologiya, 6, 3040, 1979. Shikina, N.D., I.L. Khodakovsky, and N.A. Ozerova, New data on forms of mercury transfer by hydrothermal solutions, in Geochemistry of ore formation processes [in Russian], 137160, Nauka, Moscow, 1982. Sorokin, V.I., V.A. Pokrovsky, and T.P. Dadze, Physicochemical conditions of Sb-Hg mineralization [in Russian], 144 pp., Nauka, Moscow, 1988. Torgersen, T., and W.J. Jenkins, Helium isotopes in geothermal systems: Iceland. The Geysers, Raft River and Steamboat Springs, Geochim. Cosmochim. Acta, 46, 739745, 1981. Torgersen, T., J.E. Lupton, D.C. Sheppard, and W.F. Giggenbuch, Helium isotope variations in thermal areas of New Zealand, J. Volcan. Geotherm. Res., 12, 283294, 1982. Received 23 June 2006

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